US5925707A - Oil gel formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers - Google Patents
Oil gel formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers Download PDFInfo
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- US5925707A US5925707A US08/903,526 US90352697A US5925707A US 5925707 A US5925707 A US 5925707A US 90352697 A US90352697 A US 90352697A US 5925707 A US5925707 A US 5925707A
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- Prior art keywords
- oil
- polymer
- styrene
- weight
- butadiene
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- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 19
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 title abstract description 8
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 title abstract description 5
- 238000009472 formulation Methods 0.000 title description 15
- -1 vinyl aromatic hydrocarbons Chemical class 0.000 claims abstract description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 229920001400 block copolymer Polymers 0.000 claims abstract description 8
- 150000001993 dienes Chemical class 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000004606 Fillers/Extenders Substances 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 12
- 229920000098 polyolefin Polymers 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 description 79
- 239000003921 oil Substances 0.000 description 41
- 239000000499 gel Substances 0.000 description 29
- 238000011925 1,2-addition Methods 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 229920002633 Kraton (polymer) Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229960004132 diethyl ether Drugs 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical class C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
Definitions
- This invention relates to oil gel compositions for use as filling compounds in wire and cable applications. More particularly, this invention relates to such compositions containing new high vinyl content hydrogenated styrene-butadiene-styrene (SEBS) block copolymers and to the polymers themselves.
- SEBS hydrogenated styrene-butadiene-styrene
- the oil gel must possess some degree of slump resistance at high service temperatures. Additionally, the gel needs to be strippable so that installers and repairmen can make electrical splices easily in the field. Also, the oil gel should have a good working viscosity in the melt so it can be easily pumped into the cable.
- Filling compounds used to prevent the ingress of water into telecommunications cable must have processing characteristics which allow the material to penetrate and fill the voids between densely packed insulated conductors. Application viscosity is critical and the ability to adjust the viscosity by temperature is limited by potential damage to the insulation on the copper conductors. Once the cable is filled, the filling compound must not flow out at temperatures of up to 80° C., must withstand significant heads of water, should have good craft handling characteristics, must be compatible with other components in the cable system such as splice encapsulants, and should not significantly add to the stiffness of the cable.
- KRATON® G1650, G1726, and G1652 polymers are used in the cable filling industry.
- KRATON® G1650 and G1652 polymers possess good strippability benefits (as measured by oil gel tear strengths), and are of low enough viscosity to pump into the cable and fill all the crevices between bundles of wire in cables.
- the major problem with KRATON® G1650 and G1652 polymers is that these polymers in oil gel formulations do not perform well at high service temperatures. This is due to the relatively low molecular weight of the polystyrene endblocks.
- KRATON® G 1651 and G1654 polymers show promise for excellent service temperature performance.
- the large styrene endblocks are much more resistant to flow (and loss of elasticity), thus giving high service temperature performance.
- the large endblocks also help produce oil gels which, under some conditions, can be difficult to strip (high tear resistance), and prevent flow at service temperatures.
- oil gels based on KRATON® G1651 and G1654 polymers have poor adhesion and their viscosity is too high at application temperatures to allow the gel to flow properly between the bundles of wires in a cable. Therefore, KRATON® G1651 and G1654 polymers is not used extensively in cable filling applications.
- This invention provides the advantages of both low molecular weight polymers and higher molecular weight polymers while minimizing their disadvantages.
- Using the high vinyl content polymers of the present invention in an oil gel application allows oil gel formulators to manufacture gels with high service temperature properties in a strippable and pumpable form.
- high service temperatures and a reduction of application viscosity may be mutually exclusive for oil gels.
- This invention provides a novel way to produce compositions which exhibit both of these characteristics.
- Using high vinyl content polymers as opposed to the lower vinyl content polymers discussed above fortifies the viscosity/concentration relationship of the polymers, i.e. lower viscosity with other properties remaining about the same.
- This invention provides oil gel compositions which comprise a hydrogenated styrene-butadiene-styrene (SEBS) block copolymer which has an overall weight average molecular weight of from 30,000 to 300,000, (preferably 40,000 to 220,000 and most preferably 60,000 to 220,000), a styrene block weight average molecular weight of from 4,000 to 35,000, (preferably 6000 to 33,000 and most preferably 9000 to 33,000), and a vinyl content of at least 45% by weight (% wt), preferably 45 to 90%, and an oil and, optionally, thickeners such as polyolefin wax, silica gel, fumed silica, fatty acid soaps and extender liquids such as poly(alpha-olefins). For every 100 parts by weight of copolymer, there should be at least 900 parts of oil or a mixture of oil and a polyethylene wax and/or an extender liquid.
- SEBS hydrogenated styrene-butadiene-s
- the endblocks of these novel copolymers are polymer blocks of styrene.
- Other vinyl aromatic hydrocarbons including alphamethyl styrene, various alkyl-substituted styrenes, alkoxy-substituted styrenes, vinyl naphthalene, vinyl toluene and the like, can be substituted for styrene and are expressly included in this invention.
- the butadiene used herein must produce a polymer block with a high vinyl content.
- the percent of 1,2 addition of the butadiene should be at least 45% wt, preferably 45 to 90%, more preferably 60 to 90%, and most preferably 65 to 80%.
- polymer viscosity is similar to conventional polymers and there is no advantage. Above 90% the viscosity decrease has reached a plateau and no longer drops with higher 1,2 content; therefore, there is no further advantage.
- vinyl content refers to the fact that a conjugated diene is polymerized via 1,2-addition (in the case of butadiene--it would be 3,4 addition in the case of isoprene). Although a pure "vinyl" group is formed only in the case of 1,2 addition polymerization of 1,3 butadiene, the effects of 3,4 addition polymerization of isoprene (and similar addition for other conjugated dienes) on the final properties of the block copolymer will be similar.
- vinyl refers to the presence of a pendant vinyl group on the polymer chain. The chain branching thus introduced reduces the length of the main polymer backbone, since some of the carbons in the diene are in the pendant groups. The shorter chain length reduces polymer viscosity. The pendant groups reduce ability of the polymer molecules to form crystalline structures.
- B represents polymerized units of one or more conjugated diene hydrocarbons such as butadiene or isoprene
- A represents polymerized units of one or more vinyl aromatic compounds such as styrene
- X is the residue of a monolithium initiator such as sec-butyllithium
- Y is the residue of a dilithium initiator such as the diadduct of sec-butyllithium and m-diisopropenylbenzene.
- the anionic polymerization of the conjugated diene hydrocarbons is typically controlled with structure modifiers such as diethylether or ethyl glyme (1,2-diethoxyethane) to obtain the desired amount of 1,2-addition.
- structure modifiers such as diethylether or ethyl glyme (1,2-diethoxyethane)
- diethylether or ethyl glyme (1,2-diethoxyethane structure modifiers
- diethylether or ethyl glyme (1,2-diethoxyethane structure modifiers
- ethyl glyme 1,2-diethoxyethane
- One of the benefits of polymers of high vinyl content as defined in this specification is improved clarity of oil gels containing such polymers. This is a particularly valuable characteristic for oil gels formulated for applications requiring good appearance.
- the improvement derives from the reduced concentration of crystalline polyethylene which is formed when butadiene polymerizes in the 1,4 (head-to-tail) orientation repeatedly and is hydrogenated to polyethylene. Concentration of polyethylene crystals decreases with increasing 1,2 addition (i.e., vinyl content) and goes to zero above about 55% vinyl content.
- the polymers useful in this invention may be prepared by contacting the monomer or monomers with an organoalkali metal compound in a suitable solvent at a temperature within the range from -150° C. to 300° C., preferably at a temperature within the range from 0° C. to 100° C.
- organolithium compounds having the general formula:
- R is an aliphatic, cycloaliphatic, alkyl-substituted cycloaliphatic, aromatic or alkyl-substituted aromatic hydrocarbon radical having from 1 to 20 carbon atoms.
- Suitable solvents include those useful in the solution polymerization of the polymer and include aliphatic, cycloaliphatic, alkyl-substituted cycloaliphatic, aromatic and alkyl-substituted aromatic hydrocarbons, ethers and mixtures thereof.
- Suitable solvents include aliphatic hydrocarbons such as butane, pentane, hexane, heptane and the like, cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane and the like, alkyl-substituted cycloaliphatic hydrocarbons such as methylcyclohexane, methylcycloheptane and the like, aromatic hydrocarbons such as benzene and the alkyl-substituted aromatic hydrocarbons such as toluene, xylene and the like and ethers such as tetrahydrofuran, diethylether, di-n-butyl ether and the like.
- aliphatic hydrocarbons such as butane, pentane, hexane, heptane and the like
- cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane and the like
- the hydrogenation of these polymers may be carried out by a variety of well established processes including hydrogenation in the presence of such catalysts as Raney Nickel, noble metals such as platinum, palladium and the like and soluble transition metal catalysts.
- Suitable hydrogenation processes which can be used are ones wherein the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the present of a soluble hydrogenation catalysts.
- Such processes are disclosed in U.S. Pat. Nos. 3,113,986, 4,226,952 and U.S. Pat. No. Reissue 27,145, the disclosures of which are herein incorporated by reference.
- the polymers are hydrogenated in such a manner as to produce hydrogenated polymers having a residual unsaturation content in polydiene blocks of less than about 1 percent, and preferably as close to 0 percent as possible, of their original unsaturation content prior to hydrogenation.
- a titanium catalyst such as disclosed in U.S. Pat. No. 5,039,755, which is herein incorporated by reference, may also be used in the hydrogenation process.
- the molecular weights of linear polymers or unassembled linear segments of polymers such as mono-, di-, triblock, etc., or the arms of star polymers before coupling are conveniently measured by Gel Permeation Chromatography (GPC), where the GPC system has been appropriately calibrated.
- GPC Gel Permeation Chromatography
- the polymer is essentially monodisperse (weight average molecular weight/number average molecular weight ratio approaches unity), and it is both convenient and adequately descriptive to report the "peak" molecular weight of the narrow molecular weight distribution observed. Usually, the peak value is between the number and the weight average.
- the peak molecular weight is the molecular weight of the main species shown on the chromatograph.
- the weight average molecular weight should be calculated from the chromatograph and used.
- the materials used in the columns of the GPC are styrene-divinyl benzene gels or silica gels.
- the solvent is tetrahydrofuran and the detector is a refractive index detector.
- the invention accordingly provides an oil gel composition
- a styrene-alkylene-styrene block copolymer whose polyalkylene blocks comprise ethylene/butylene units and an oil
- optionally may include a polyolefin wax and/or an extender liquid which liquid is a poly(alpha-olefin) and extends and softens the polybutadiene blocks of the copolymer.
- pbw 100 parts by weight
- No more than 4900 pbw wax/oil/extender liquid per 100 parts polymer can be used or the polymer will not thicken the composition properly and will not retain oil well enough to prevent oil bleed during service. More preferably, the amount is 1400 to 4850 pbw and most preferably, it is 1600 to 2500.
- the oils which can be used include, for example, paraffinic oils, mineral oils, naphthenic oils, and those available from Shell Oil Company under its trademark SHELLFLEX®, Kaydol oil produced by Witco, and Fina Chemicals under the trade mark Vestan A360B. Drakeol 34 oil from Penreco and Witco 380P0 oil from Witco can also be used. If it is used, the extender liquid will generally make up at least 5% wt of the total oil/extender liquid portion but no more than about 50% wt because the polymer may not be able to retain larger proportions due to limited compatibility.
- the polyolefin wax component of oil gels if used, generally is low molecular weight polyethylene. Suitable grades are manufactured by Allied under the A-C trade name, by Quantum Chemical under Petrothene, and Eastman Chemical Products under Epolene.
- the content of polyethylene wax is usually 3 to 10% of the total composition. More than 10% reduces the oil retention capability of the composition and less than 3% increases the cost of the polymer package.
- the poly(alpha-olefin) extender liquids useful in the compositions of this invention comprising the block copolymer may be selected from those available by simple trial and error. Examples include those available from Ethyl Corporation under the trade mark "Ethylflo".
- the extenders preferably have a minimum boiling point higher than the softening point of the block copolymer. Commercially available grades include "Ethylflo 164", “Ethylflo 166", “Ethylflo 168", and "Ethylflo 170".
- compositions are generally prepared by mixing the oil and the polymer together with some kind of mechanical mixing aid and optionally with the aid of a volatile solvent.
- the extender liquid When the extender liquid is used, it is usually mixed with these components at a temperature not less than the glass transition temperature of the polystyrene blocks of the copolymer. It may be useful to use various additives such as stabilizers, antioxidants, tackifiers, and the like.
- PP5181 is an SEBS Block copolymer with a high vinyl content. Its molecular characteristics are compared with those of Polymer A in Table 1 below. It can be seen that they are very similar except for the vinyl content. The other polymers have different characteristics.
- PP5828 shown below, is similar to Polymer B except 78% of its rubber block is in a 1,2 microstructure, compared to 38% for Polymer B.
- the flow properties of PP5828 are dramatically better than Polymer B as indicated by solution viscosity (two orders of magnitude lower) and much higher melt flow indices.
- PP5823 (78% 1,2 addition) exhibits much better flow properties than Polymer C, which has 38% 1,2 addition.
- PP5819 has an intermediate level of 1,2 structure (47%), but is still markedly better in flow properties than Polymer C.
- the high flow characteristics mean that pumpability of oil gel formulations made from high vinyl polymers is far superior to conventional block polymers.
- the oil gel samples for Formulation #1 were prepared by adding 6% by weight of polymer to Kaydol mineral oil in a Silverson mixer @ 100 degrees Centigrade. The samples were mixed until fully dissolved and poured out into a release lined boat to approximately 0.2 inches thick. When problems existed during mixing that prevented good incorporation of the polymer, temperature was raised in the mixer until a uniform mixture was achieved. Samples were then cut and tested for tear resistance in accordance with ASTM method D624.
- the oil gel samples for Formulation #2 were prepared by adding 6% by weight of polymer to Kaydol mineral oil in a Silverson mixer @ 100 degrees Centigrade. Additionally, 6% AC9 polyethylene wax was added to the formulation. The samples were mixed until fully dissolved and poured out into a release lined boat to approximately 0.2 inches thick. When problems existed during mixing that prevented good incorporation of the polymer in the oil, the temperature was raised in the mixer until uniform mixing was achieved. Samples were then cut and tested for tear resistance in accordance with ASTM method D624. Melt viscosities were run on selected gels. Additionally, DMA temperature sweeps were run to determine the temperature at which the gel began to fall apart (via elastic modulus loss).
Abstract
Description
RLi
TABLE 1 ______________________________________ Vinyl Styrene Content of content of Block MWs, butadiene whole Polymer Polymer MW 1000's block polymer ______________________________________ PP5181 205,800 27.5-144.6-33.5 75.2% 26.3% Polymer A 181,000 29.0-123-29.0 38% 32% PP5828 56,000 10-39-10 78% 29.6% Polymer B 67,000 10-47-10 38% 29.9% PP5823 35,000 6-23-6 78% 29.3% PP5819 38,000 6-26-6 47% 29.5% Polymer C 50,000 7.5-35-7.5 38% 30% Polymer D 126,000 19-89-19 35% 30% ______________________________________
TABLE 2 ______________________________________ Glass Transition Toluene Temp° C. Soln. Visc. Melt Flow Index, g/10 min Rubber Polymer 25° C., cps 200° C., 5 kg 230° C., 5kg Block ______________________________________ PP5181 70 (10% solids) -- -- -38 Polymer 1850 (10% solids) <1 <1 -58 PP5828 99 (25% solids) 9.7 48.4 -32 Polymer 9610 (25% solids) <1 <1 -58 B PP5823 37 (25% solids) 359 >400 -32 PP5819 389 (25% solids) 19.9 83 -52 Polymer 1670 (25% solids) <1 5.7 -58 C ______________________________________
TABLE 3 ______________________________________ Tear Tear Melt Strength Strength Viscosity Formulation Formulation Formulation Approx. Temp. #1 #2 #2 of Elasticity Loss Polymer (lb/in) (lb/in) at 350° F. Formulation #2 ______________________________________ Polymer A 1.937 5.204 15,000 cps 90-95° C. 1.637 Polymer D 1.435 3.441 200 cps 85-90° C. Polymer B -- 1.017 23 cps 75-80° C. Polymer C 0.138 0.967 20 cps 60-70° C. PP-5181 0.189 0.884 1200 cps 90-95° C. ______________________________________ Notes: 1. Tear Strength determined by ASTM method D624, using 0.2 inch thick oil gels. Each value above is the average of 4-8 tests. 2. Formulation 1 contains 6% polymer, and 94% Kaydol oil. 3. Formulation 2 contains 6% Polymer, 6% PE Wax (AC9 manufactured by Alied), and 88% Kaydol Oil. 4. The approximate temperature of elasticity loss is determined at the temperature at which the elastic modulus of the oil gel (as measured by DMA) drops off.
Claims (4)
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